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EP2111104A2 - Concentre de suspension huileuse comprenant des substances actives agrochimiques micro-encapsulees - Google Patents

Concentre de suspension huileuse comprenant des substances actives agrochimiques micro-encapsulees

Info

Publication number
EP2111104A2
EP2111104A2 EP08701053A EP08701053A EP2111104A2 EP 2111104 A2 EP2111104 A2 EP 2111104A2 EP 08701053 A EP08701053 A EP 08701053A EP 08701053 A EP08701053 A EP 08701053A EP 2111104 A2 EP2111104 A2 EP 2111104A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
methyl
active ingredients
suspension concentrate
oil suspension
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08701053A
Other languages
German (de)
English (en)
Inventor
Ralph Grohs
Roland Deckwer
Frank Rosenfeldt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Bayer CropScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Priority to EP08701053A priority Critical patent/EP2111104A2/fr
Publication of EP2111104A2 publication Critical patent/EP2111104A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

Definitions

  • Oil suspension concentrate with microencapsulated agrochemical active ingredients Oil suspension concentrate with microencapsulated agrochemical active ingredients
  • the invention relates to oil suspension concentrates for crop protection and agrochemical active substances contained therein, which are present in encapsulated form.
  • Microcapsule is therefore to be distinguished from other forms of formulations such as emulsion, microsphere, liposome, since these do not have the physical separation characteristic of liquids through a wall made of polymers.
  • oil-in-water microencapsulation there is an oil-in-water emulsion, i. the water-immiscible or water-insoluble material is surrounded by the polymer material of the microcapsule.
  • the aqueous phase is inside the microcapsule. It is therefore also referred to as "inverse microencapsulation”.
  • the present invention predominantly uses water-in-oil microencapsulation unless the multi-microencapsulation process is employed.
  • MuJti microencapsulation a distinction must be made between “water-in-oil-in-water microencapsulation” and “water-in-oil-in-oil microencapsulation”.
  • the implementation of both techniques is possible, wherein the water-in-oil-in-oil microencapsulation is in the foreground.
  • the mentioned forms of microencapsulation are appropriate
  • the formation of the microcapsules takes place from the monomers and prepolymers contained in the oil droplets under the influence of heat and / or by pH change and / or by mechanical stirring.
  • the respective treatment causes the polymerization of the monomer or the prepolymers.
  • EP 1 282 353 B1 discloses the combination of pesticides with organic or inorganic carrier materials for the controlled release of the active ingredients, whereby the use of the oil-in-water microencapsulation is also provided.
  • the disclosed combinations allow for the suppression of antagonization of other drugs in admixture therewith and, at the same time, eliminate the need for time and labor intensive splinter applications.
  • the problem of chemical incompatibility between drugs is not the subject of EP 1 282 353 B1.
  • Water-in-oil microcapsules are prepared from a water-in-oil emulsion by the "water-in-oil process.” Such a process is disclosed in US Patent US 4,157,983 A corresponding process using two monomers and prepolymers is in US Pat. No. 4,534,783.
  • a process for multiple microencapsulation is disclosed in WO 2005/058476 A1. It is a continuous process for microencapsulation of water-in-oil-in-water by in situ interfacial polymerization of the corresponding emulsion.
  • the active compounds included in the microcapsules are beneficial to health and suitable for other biological purposes.
  • the use of the method for the formulation of agrochemical active substances or for the solution of the problem of chemical incompatibility between agrochemical active ingredients is not provided for.
  • Another particular method for "water-in-oil microencapsulation" is disclosed in WO 98/28957 A.
  • the wall of the microcapsules in the presence of an active surface proton transfer proton catalyst by in situ self-condensation of prepolymers which
  • Oil-soluble herbicides include EPTC, butylates, cycloates, molinates, vernolates, acetochlor, metolachlor, alachlor, butachlor, propachlor and trifluralin.
  • the hydrolysis sensitivity always has to be considered when formulating active substances from the class of sulfonylureas.
  • Their chemical stability is very well ensured by the previously established forumulation techniques, provided that the sulfonylureas are used as a single active ingredient or in combination with other sulfonylureas or with safener.
  • a challenge remains the formulation of sulfonylureas in combination with active ingredients or excipients whose structure has an acid function and / or free OH groups.
  • Agents known for their hydrolysis-inducing potential over sulfonylureas are e.g. Glufosinate and glyphosate.
  • the low pH of glyphosate ( ⁇ 7) is detrimental to those sulfonylureas that are stable in the basic range.
  • the chemical incompatibility of drugs is a complex problem.
  • the stability of the active ingredient after dilution of the concentrate in the spray tank can be a problem.
  • the crystallization must be prevented and the distributability and the biological activity of the active ingredient must be ensured.
  • the object of the present invention was to provide an improved, liquid crop protection agent formulation having at least two agrochemical active ingredients, wherein each active ingredient, in particular the chemically unstable active ingredients contained in the formulation, and the formulation as a whole, a high chemical and physical stability and a have high biological effectiveness and crop plant compatibility.
  • This also generally includes the avoidance of antagonistic inactivity or overdose, which otherwise necessitates the application of splinter applications.
  • the present invention thus relates to an oil suspension concentrate containing
  • the core idea of the alternatives is to protect the more hydrolysis-sensitive active ingredient in the case of a combination of active ingredients, in any case in a microencapsulated form, another active ingredient which possibly has a hydrolysis-inducing potential.
  • oil suspension concentrates which contain at least two different agrochemical active substances, at least one of which is water-soluble and is present inside a microcapsule. At least one other, i. the active ingredient present in (b), dispersed or dissolved in the oil phase, is also encapsulated.
  • At least two active substances which differ, for example, in their solubility and / or in their hydrolysis sensitivity are microencapsulated.
  • the hydrolysis-sensitive active ingredient is additionally protected, in front of the active ingredient, which is also present in microencapsulated form due to its hydrolysis-inducing potential.
  • the additional microencapsulation of the active ingredients dispersed or dissolved better in the oil phase can additionally have the advantage that, due to the delayed release of the differently encapsulated active ingredients, splinter applications can be avoided.
  • an oil suspension concentrate which contains at least two different agrochemical active ingredients, at least one of which is present in the interior of a microcapsule and at least one in non-encapsulated form in the oil phase, wherein the present in non-encapsulated form in the oil phase active ingredient Acetolactate synthase (ALS) inhibitor.
  • ALS Acetolactate synthase
  • the third alternative uses an oil suspension concentrate containing at least two different agrochemically active compounds, at least one of which is present inside a microcapsule and at least one in an unencapsulated form in the oil phase, where the microencapsulated agent is an acetolactate synthase (ALS) inhibitor and the active ingredient having high hydrolysis-inducing potential is present in non-encapsulated form in the oil phase. That According to the approach of the third alternative, the additional microencapsulation of the hydrolysis-inducing active ingredients is dispensed with.
  • ALS acetolactate synthase
  • an oil suspension concentrate which contains at least two different agrochemical active ingredients, at least one of which is present in the interior of a microcapsule and at least one in non-encapsulated form in the oil phase, wherein in non-encapsulated form in the oil phase present active substance is a phosphorus-containing herbicide.
  • the active substances were treated according to the multi-microencapsulation method in WO 2005/058476 A1 and are present in appropriate form.
  • the most sensitive to hydrolysis active ingredient, however, is in the oil phase of the oil suspension concentrate, because there is the best protected.
  • the oil suspension concentrate contains at least two different agrochemical active ingredients, wherein at least one active ingredient is water-soluble and at least one active ingredient is dispersed or dissolved in the oil phase and the active ingredients have been treated according to a multi-microencapsulation method and present in appropriate form.
  • the class of compounds of the sulfonylureas belongs to their mode of action according to the group of ALS inhibitors. These inhibit the enzyme acetolactate synthase (ALS) and thus the protein synthesis in the plants.
  • ALS acetolactate synthase
  • oil suspension concentrate oil dispersion
  • OD oil dispersion
  • One or more active substances or safeners are suspended in the organic solvent. In this case, further active ingredients or safeners may be dissolved in the organic solvent.
  • agrochemical active ingredient in the context of this invention includes herbicides, plant growth regulators, safeners. That
  • the oil suspension concentrates according to the invention may also contain one or more safeners, it being possible for the safener to be present in microencapsulated form in addition to the active substance. Possible safeners are mentioned below by way of example in connection with the agrochemical active ingredients.
  • the oil suspension concentrates according to the invention may contain one or more inorganic salts as well as customary auxiliaries and additives.
  • herbicides examples include: herbicides
  • herbicides are e.g. ALS inhibitors (acetolactate synthetase inhibitors) or herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives and heteroaryloxy-phenoxyalkanecarboxylic acid derivatives, such as quinolyloxy, quinoxalyl-oxy, pyridyloxy , Benzoxazolyloxy- and Benzthiazolyloxyphenoxyalkan-carboxylic acid esters, cyclo-hexanedione derivatives, imidazolinones, phosphorus-containing herbicides, eg glufosinate-type or glyphosate-type, pyrimidinyloxypyridinecarboxylic acid derivatives, pyrimidyloxybenzoic acid derivatives, triazolopyrimidine-sulfonamide derivatives and S- (N
  • the herbicides from the group of carbamates, thiocarbamates, haloacetanilides are not provided as active substances present in the oily phase.
  • carbamates, thiocarbamates, haloacetanilides may be present in the aqueous phase inside the microcapsules contained in the oil suspension concentrate.
  • the herbicidal active compounds from the group of ALS inhibitors are always to be understood as meaning, in addition to the neutral compounds, their salts with inorganic and / or organic counterions.
  • sulfonylureas can form, for example, salts in which the hydrogen of the -S ⁇ 2-NH group is replaced by a cation suitable for agriculture.
  • These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts or salts with organic amines.
  • salt formation can take place by addition of an acid to basic groups, such as, for example, amino and alkylamino.
  • Suitable acids for this purpose are strong inorganic and organic acids, for example HCl, HBr, H 2 SO 4 or HNO 3 .
  • Preferred ALS inhibitors come from the series of sulfonylureas and / or their salts, for example pyrimidine or triazinylaminocarbonyl [benzene, pyridine, pyrazole, thiophene and (alkylsulfonyl) alkylamino] sulfamides.
  • sulfonylureas are, for example
  • Methyl-S-chloro- ⁇ , ⁇ , ⁇ -dimethoxypyrimidine, ⁇ -ylylcarbamoyl-sulfamoyl-O-methyl-pyrazole-4-carboxylate (EP-A 0 282 613); Methyl 5- (4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl) -1- (2-pyridyl) pyrazole-4-carboxylic acid (NC-330, see Brighton Crop Prot. Conference "Weeds 1 1991, Vol.
  • E is CH or N, preferably CH, R 20 is iodine or NR 25 R 26 ,
  • R 21 is hydrogen, halogen, cyano, (Ci-C 3) alkyl, (Ci-C 3) alkoxy, (CrC 3) - haloalkyl, (dC 3) -haloalkoxy, (C r C 3) alkylthio, ( C r C 3 ) -alkoxy- (d-
  • R x, R y are independently hydrogen, (C r C 3) alkyl, (Ci-C 3) -alkenyl, (CrC 3) - alkynyl or together are - (CH 2) 4 -, - (CH 2) 5 - or - (CH 2 ) 2 -O- (CH 2 ) 2, n is 0.1, 2 or 3, preferably 0 or 1,
  • R 22 is hydrogen or CH 3
  • R 23 is halogen, (C 1 -C 2 ) -alkyl, (-C 2) alkoxy, (CrC 2) -haloalkyl, in particular
  • R 25 is (C r C 4 ) alkyl
  • R 26 is (CrC 4 ) alkylsulfonyl or
  • R 25 and R 26 together represent a chain of the formula - (CH 2 ) 3 SO 2 - or - (CH 2 J 4 SO 2 -, for example 3- (4,6-dimethoxypyrimiden-2-yl) -1- (3 -N-methylsulfonyl-N-methyl-aminopyridin-2-yl) -sulfonylurea, or salts thereof;
  • oil suspension concentrate according to the invention is present as the herbicidal active ingredient pyridyl sulfonylurea in suspended form in the organic phase. This means that the herbicidal active ingredient pyridyl sulfonylurea in suspended form in the organic phase.
  • the pyridyl-sulfonylurea in the organic solvent to more than 50 wt .-%, more preferably more than 80 wt .-% suspended, each based on the total amount of pyridyl-sulfonylurea a) in the oil suspension concentrate according to the invention.
  • Preferred pyridyl-sulfonylureas are dioxazine-pyridylsulfonylureas, in particular of the general formula (I) wherein
  • R 11 is hydrogen, alkyl, halogen and haloalkyl
  • R 1 is hydrogen or an optionally substituted radical from the group consisting of alkyl, alkoxy, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aralkyl and aryl
  • R 2 is hydrogen, halogen or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, Alkylamino or dialkylamino each having 1 to 6 carbon atoms
  • R 3 is hydrogen, halogen or each optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino each having 1 to 6 carbon atoms
  • R 4 - R 7 are independently hydrogen , Halogen, cyano, thiocyanato or each optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulf
  • A is nitrogen or a CH group
  • R 1 is hydrogen or an optionally halogen-substituted radical from the series alkyl, alkoxy, alkoxyalkyl, alkenyl and alkynyl, each with up to
  • R 2 is hydrogen, halogen or each optionally substituted by halogen alkyl, alkoxy, alkylthio, alkylamino or dialkylamino with in each case
  • R 3 is hydrogen, halogen or each optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino with in each case
  • R 4 - R 7 are each independently hydrogen, halogen, cyano, thiocyanato or each optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl each having 1 to 3 carbon atoms in the alkyl radicals
  • R 8 represents hydrogen, halogen, cyano, thiocyanato or each optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkylcarbonyl, alkoxycarbonyl or alkylaminocarbonyl each having 1 to 3 Carbon atoms in the alkyl radicals.
  • salts which are obtained from compounds of the formula (I) and bases, such as, for example, sodium, potassium or calcium hydroxide, hydride, amide and carbonate, Sodium or potassium-CrC 4 -alkanolaten, ammonia, Ci-C 4 -alkylamines, di (CrC 4 - alkyl) -amines or tri- (CrC 4 -alkyl) -amines, obtained by conventional methods.
  • bases such as, for example, sodium, potassium or calcium hydroxide, hydride, amide and carbonate, Sodium or potassium-CrC 4 -alkanolaten, ammonia, Ci-C 4 -alkylamines, di (CrC 4 - alkyl) -amines or tri- (CrC 4 -alkyl) -amines, obtained by conventional methods.
  • A is nitrogen or a CH group
  • R 1 is hydrogen, methyl, ethyl, methoxy, methoxymethyl or ethoxy,
  • R 2 is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy,
  • R 3 is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy,
  • R 4 - R 7 are independently hydrogen, fluorine, chlorine, cyano, or each optionally substituted by chlorine or fluorine methyl, methylthio, methylsulfinyl, methylsulfonyl, methoxycarbonyl and ethoxycarbonyl, preferably hydrogen .
  • R 8 represents hydrogen, fluorine, chlorine, bromine, cyano or represents in each case optionally substituted by chlorine or fluorine methyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methyl or dimethylamino, preferably hydrogen.
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, methylamino or dimethylamino,
  • R 3 is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, methylamino or dimethylamino,
  • R 4 - R 7 is hydrogen
  • R 8 is hydrogen. Also particularly preferred are compounds of the formula (I) and salts thereof, in particular their alkali metal salts,
  • A is a CH group
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy,
  • R 3 is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, methylamino or dimethylamino,
  • R 4 - R 7 is hydrogen
  • R 8 is hydrogen
  • hydrocarbon radicals mentioned in the radical definitions such as alkyl, alkenyl or alkynyl, also in combinations with heteroatoms, such as in alkoxy, alkylthio, haloalkyl or alkylamino, are also straight-chain or branched, even if not expressly stated.
  • the pyridylsulfonylureas may also be present as salts, e.g. as metal salts such as alkali (e.g., Na, K) salts or as alkaline earth (e.g., Ca, Mg) salts or as ammonium or organic amine salts.
  • metal salts such as alkali (e.g., Na, K) salts or as alkaline earth (e.g., Ca, Mg) salts or as ammonium or organic amine salts.
  • Such salts are readily obtained by conventional salt formation techniques, for example, by dissolving or dispersing a pyridylsulfonylurea, e.g. of the formula (I), in a suitable diluent, e.g. Methylene chloride, acetone, tert-butyl methyl ether or toluene, and addition of a suitable base.
  • the salts can then - be isolated by concentration or suction
  • (+) The indicated melting point (mp) refers in each case to the corresponding sodium salt, ie the corresponding compound in which the hydrogen of the -S ⁇ 2 -NH group has been replaced by sodium.
  • the herbicidal active compounds from the series of pyridyl-sulfonylureas are in the oil suspension concentrates according to the invention generally in amounts of 0.01 to 50% by weight, preferably 0.1 to 30% by weight, the term "% by weight” here and throughout the specification, unless otherwise defined, refers to the relative weight of the respective component on the total weight of the formulation.
  • Alkoxyphenoxysulfonylureas as e.g. in EP-A 0 342 569, preferably those of the formula
  • E is CH or N, preferably CH
  • R 27 is ethoxy, propoxy or isopropoxy
  • R 28 is halogen, NO 2, CF 3, CN, (Ci-C 4) -alkyl, (C 1 -C -alkoxy, (C r C4) -alkylthio or (CrC 3) alkoxy-carbonyl, preferably in 6-position on the phenyl ring, n is 0, 1, 2 or 3, preferably 0 or 1, R 29 is hydrogen, (C r C4) alkyl or (C 3 -C 4) alkenyl,
  • R 30, R 31 independently of one another are halogen, (dC 2) alkyl, (Ci-C 2) alkoxy, (Ci-C 2) - haloalkyl, (dC 2) -haloalkoxy or (Ci-C 2) alkoxy (C 1 -C 2 ) -alkyl, preferably OCH 3 or CH 3 , for example 3- (4,6-dimethoxypyrimidin-2-yl) -1- (2-ethoxyphenoxy) sulfonylurea, or salts thereof;
  • imidazolylsulfonylureas e.g.
  • MON 37500 sulfosulfuron (see Brighton Crop Prot. Conf., Weeds', 1995, p. 57), and other related sulfonylurea derivatives and mixtures thereof;
  • Typical representatives of these active ingredients include the following compounds: amidosulfuron, azimsulfuron, Bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, Cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, Flupyrsulfuron-methyl-sodium, halosulfuron-methyl, imazosulfuron , Metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron Methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, iodosulfuron-methyl and its sodium salt (WO
  • Examples of compounds from the group of the phenylsulfonylaminocarbonyl-triazolinones are e.g. Flucarbazone or propoxycarbazone and / or salts thereof.
  • Q 1 is O (oxygen) or S (sulfur),
  • Q 2 is O (oxygen) or S (sulfur),
  • R 1 is optionally substituted by cyano, halogen or -C 4 -alkoxy-substituted alkyl having 1 to 6 carbon atoms, represents optionally cyano- or halogen-substituted alkenyl or alkinyl each having 2 to 6 carbon atoms, represents in each case optionally cyano-, halogen or CIC t Alkyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, in each case optionally by nitro, cyano,
  • R 3 is hydrogen, hydroxyl, mercapto, amino, cyano, fluorine, chlorine, bromine, iodine, optionally substituted by fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylcarbonyl or C 1 -C 4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms, represents in each case optionally substituted by fluorine, chlorine and / or bromine-substituted alkenyl or alkinyl each having 2 to 6 carbon atoms, represents in each case optionally substituted by fluorine, chlorine, cyano, C- ⁇ -C 4 Alkoxy or C 1 -C 4 -alkoxycarbonyl-substituted alkoxy, alkylthio, alkylamino or alkylcarbonylamino having in each case 1 to 6 carbon atoms in the alkyl group, for alkenyl
  • Alkinyl group for dialkylamino having in each case 1 to 4 carbon atoms in the alkyl groups, for each optionally substituted by methyl and / or ethyl aziridino, pyrrolidino, piperidino or morpholino, each optionally substituted by fluorine, chlorine, bromine, cyano and / or dC 4 alkyl substituted cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkylthio,
  • Cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylthio or cycloalkylalkylamino having in each case 3 to 6 carbon atoms in the cycloalkyl or cycloalkenyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, or in each case optionally by fluorine, chlorine, bromine, cyano, nitro, C 1 -C 4 Alkyl, trifluoromethyl, C r C 4 alkoxy and / or C 1 -C 4 -
  • R 4 is hydrogen, C 1 -C 4 -alkyl, hydroxy, amino, cyano, C 2 -C -alkylamino-amino, optionally substituted by fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkoxy, C 1 -C 4- alkylcarbonyl or C 1 -C 6 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms, in each case optionally substituted by fluorine, chlorine and / or bromine-substituted alkenyl or alkynyl having in each case
  • R 3 and R 4 together represent optionally branched alkanediyl having 3 to 6 carbon atoms
  • phenoxyphenoxy- and benzyloxyphenoxy-carboxylic acid derivatives e.g. Methyl 2- (4- (2,4-dichlorophenoxy) phenoxy) propionate (diclofopmethyl), 2- (4- (4-bromo-2-chlorophenoxy) phenoxy) propionate (DE-A 26 01 548) Methyl 2- (4- (4-bromo-2-fluorophenoxy) -phenoxy) -propionate (US Pat. No. 4,808,750), 2- (4- (2-chloro-4-trifluoromethylphenoxy) -phenoxy) -propionic acid methyl ester (DE-A 24 33 067),
  • thiocarbamates e.g. S-ethyl-N, N-dipropylthiocarbamate (EPTC), S-ethyl-N, N-diisobutylthiocarbamate (butylate);
  • imidazolinones e.g. Methyl 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methylbenzoate and 2- (4-isopropyl-4-methyl-5-oxo-2-imidazoline-2 yl) -4-methylbenzoic
  • Triazolopyrimidine sulfonamide derivatives e.g. N- (2,6-Difluorophenyl) -7-methyl-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide
  • salts preferably acid addition salts of the compounds, for example their hydrochlorides.
  • L) phosphorus-containing herbicides e.g. one or more compounds of the formula (IV) or derivatives thereof, such as salts,
  • active compounds of the formula (IV) and (V) are the following:
  • auxins and auxin analogs e.g. 4-indole-3-butyric acid, indole-3-acetic acid, 1-naphthylacetic acid, 2- (1-naphthyl) acetamide and 2-naphthyloxyacetic acid;
  • cytokinins e.g. Kinetin and 6-benzylaminopurine
  • gibberellins e.g. Gibberillic Acid, Gibberillin A4 and A7;
  • T) ethylene precursors e.g. ethephon
  • V) ureas e.g. Chlorotoluron, dimefuron, diuron, fluometuron, isoproturon, isourone, carbutilate, linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron and tebuthiuron and
  • hydroxybenzonitriles e.g. such as bromoxynil and loxynil and their salts and esters such as bromoxyniloctanoate and loxyniloctanoate.
  • the agrochemical active substances can also be growth regulators. Examples of these are terbufos, cyclanilides and thidiazuron.
  • herbicides plant growth regulators
  • groups A to X for example, from the above-mentioned writings and / or from "The Pesticide Manual", 12th edition (2000) and 13th edition (2003), The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides - “, by WT. Thompson, Thompson Publications, Fresno CA, USA 1990 and “Farm Chemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA, 1990. safener
  • the agrochemical active substances can also be safeners. Examples include:
  • n ' is a natural number from 0 to 5, preferably 0 to 3
  • T is a (Ci or C2) alkanediyl chain which is unsubstituted or substituted by one or two (C 1 -C 6 -alkyl radicals or by [(C 1 -C 3 ) -alkoxy] carbonyl;
  • W is an unsubstituted or substituted divalent heterocyclic radical from the group of unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero ring N or O atoms, at least one N atom and at most one O atom in the ring, preferably a radical from the group (W1) to (W4),
  • R 17 , R 19 are the same or different halogen
  • R 18 , R 20 are identical or different OR 24 , SR 24 or NR 24 R 25 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S. which is connected via the N atom to the carbonyl group in (S-II) or (S-III) and unsubstituted or by radicals from the group (C 1 -C 4 ) alkyl,
  • R 24 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 C atoms;
  • R 25 is hydrogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy or substituted or unsubstituted phenyl, R x is H 1 (C r C 8 ) alkyl, C r C 8 (haloalkyl), (C 1 -C 4 ) alkoxy (C 1 -C 8 ) alkyl, cyano or
  • R 26 is hydrogen, (Ci-C 8 ) alkyl, (C r C 8 ) haloalkyl, (C r C 4 ) alkoxy (C r C 4 ) alkyl, (Ci-C 6 ) hydroxyalkyl, (C C 3 -C 12 ) is cycloalkyl or tri (C 1 -C 4 ) alkylsilyl;
  • R 27 , R 28 , R 29 are identical or different hydrogen, (C r Cs) alkyl,
  • R 21 is (C r C 4 ) alkyl, (C r C 4 ) haloalkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) haloalkenyl,
  • R 22 , R 23 is identical or different hydrogen, (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl,
  • R 30 is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a hydrocarbylthio radical or a heterocyclyl radical which is preferably bonded via a carbon atom, where each of the last-mentioned 4 radicals is unsubstituted or substituted by one or more identical or different radicals from the group halogen, cyano, nitro , Amino, hydroxy, carboxy, formyl, carbonamide, sulfonamide and radicals of the formula -Z a -R a is substituted, wherein each hydrocarbon moiety preferably 1 to 20 carbon atoms and a C-containing radical R 30 including substituents preferably 1 to 30 Having C atoms;
  • R 31 is hydrogen or (C 1 -C 4) alkyl, preferably hydrogen, or R 30 and R 31 together with the group of the formula -CO-N- represent the radical of a 3- to 8-membered saturated or unsaturated ring;
  • R 32 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, formyl, CONH 2 , SO 2 NH 2 or a radical of the formula -Z b -R b ;
  • R 33 is hydrogen or (C 1 -C 4 ) -alkyl, preferably H;
  • R 34 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, CHO, CONH 2 , SO 2 NH 2 or a radical of the formula -Z c -R c ;
  • R a is a hydrocarbon radical or a heterocyclyl radical, where each of the two last-mentioned radicals is unsubstituted or substituted by one or more identical or different radicals from the group halogen, cyano, nitro,
  • R b , R c are a hydrocarbon radical or a heterocyclyl radical, where each of the latter two radicals is unsubstituted or substituted by one or more identical or different radicals from the group halogen, cyano, nitro, amino, hydroxyl, phosphoryl, halogen (C 1 -C 4) alkoxy, mono- and di - [(C 1 -C 4 ) alkyl] amino, or an alkyl radical in which several, preferably 2 or 3, non-adjacent CH 2 groups are each replaced by an oxygen atom;
  • Z a is a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-,
  • Z b , Z c independently of one another a direct bond or a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO-, -SO 2 -, -NR * -, -SO 2 -NR * -, -NR * -SO 2 -, -CO-NR * - or -NR * -CO-, where the bond of the respective divalent group indicated on the right is the bond to the radical R b or R c and where the R * in the last-mentioned 5 radicals are each independently H, (C 1 -C 4 ) -alkyl or halo (C r C 4 ) -alkyl; n is an integer from 0 to 4, preferably 0, 1 or 2, in particular O or 1, and m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1
  • R 30 cyclopropyl
  • R 34 2-OMe is (V-3)
  • R 30 cyclopropyl
  • R 34 2-OMe-5-CI is (V-4)
  • R 30 cyclopropyl
  • R 34 2-Me is (V-5)
  • X 3 is CH or N
  • R 35 is hydrogen, heterocyclyl or a hydrocarbon radical, where the latter two radicals are optionally substituted by one or more, identical or different radicals from the group halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH 2 , SO 2 NH 2 and Z a -R are a substituted;
  • R 36 is hydrogen, hydroxy, (Ci-C 6) -alkyl, (C 2 -C 6) alkenyl, (C 2 -C 6) -alkynyl, (CrC 6) - alkoxy, (C 2 -C 6) - Alkenyloxy, where the five last-mentioned radicals are optionally substituted by one or more, identical or different radicals from the group halogen, hydroxy, (C 1 -C 4 -alkyl, (C 1 -C 4 -alkoxy and (C 1 -C 4 ) -alkylthio, or
  • R 35 and R 36 together with the nitrogen atom carrying them have a 3- to 8-membered saturated or unsaturated ring;
  • R 37 is halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH 2 , SO 2 NH 2 or Z b -R b ;
  • R 38 is hydrogen, (C r C4) alkyl, (C 2 -C 4) -alkenyl or (C 2 -C 4) alkynyl;
  • R 39 is halogen, cyano, nitro, amino, hydroxy, carboxy, phosphoryl, CHO, CONH 2 ,
  • R a is a (C 2 -C 2 0) -alkyl radical whose carbon chain is mono- or polysubstituted
  • R b, R c are identical or different and are a (C 2 -C 2 o) -alkyl radical whose carbon chain one or more times interrupted by oxygen atoms, is heterocyclyl or a hydrocarbon radical, where the last two radicals optionally substituted by one or more identical or different Radicals from the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, (CrC 4 ) - haloalkoxy, mono- and di - [(Ci-C 4 ) alkyl] amino substituted;
  • Z a is a divalent unit selected from O, S, CO, CS, C (O) O, C (O) S, SO, SO 2 , NR d , C (O) NR d or SO 2 NR d ;
  • Z b , Z c identically or differently, represent a direct bond or a divalent unit from the group O 1 S, CO, CS, C (O) O, C (O) S, SO, SO 2 , NR d , SO 2 NR d or C (O) NR d ;
  • R d is hydrogen, (C r C 4 ) -alkyl or (C r C 4 ) -haloalkyl;
  • n is an integer from 0 to 4, and in the case that X is CH, an integer from 0 to 5, and in the case where X is N, an integer from 0 to 4; preferably safeners of compounds of the formula (S-VI) in which X 3 CH;
  • R 35 is hydrogen, (C r C6) alkyl, (C 3 -C 6) -cycloalkyl, (C 2 -C 6) alkenyl, (C 5 -C 6) - cycloalkenyl, phenyl or 3- to 6 hetero-cyclic heterocyclyl having up to three heteroatoms from the group of nitrogen, oxygen and sulfur, where the six last-mentioned radicals are optionally substituted by one or more, identical or different substituents from the group halogen, (C 1 -C 6 ) -
  • R 36 is hydrogen, (C r C 6 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, where the last three radicals mentioned are optionally substituted by one or more, identical or different substituents from the group Halogen, hydroxy, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy and
  • R 38 is hydrogen; R39 is halogen, nitro, (C r C4) alkyl, (C "
  • R ⁇ and R ⁇ independently of one another represent hydrogen, C 1 -C 6 -alkyl, C 5 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl,
  • R ⁇ and R ß together are a C 4 -C 6 alkylene or by oxygen, sulfur, SO, SO 2, NH or -N (-C 4 alkyl) - interrupted C 4 -C 6 - alkylene bridge,
  • R ⁇ is hydrogen or C 1 -C 4 -alkyl
  • R a and R b independently of one another represent hydrogen, halogen, cyano, nitro,
  • R 9 and R h independently of one another represent hydrogen, halogen, C 1 -C 4 -alkyl, trifluoromethyl, methoxy, methylthio or -COOR ', where
  • R c is hydrogen, halogen, C 1 -C 4 -alkyl or methoxy
  • R d is hydrogen, halogen, nitro, C r C 4 alkyl, C 1 -C 4 -alkoxy, C r C 4 alkylthio, C r C 4 - alkylsulfinyl, C r C 4 alkylsulfonyl, -COOR j or -CONR k R m ,
  • R e is hydrogen, halogen, C r C 4 alkyl, -COOR j, trifluoromethyl or methoxy, or R d and R e together represent a C 3 -C 4 alkylene bridge,
  • R f is hydrogen, halogen or C 1 -C 4 -alkyl
  • R x and R ⁇ independently represent hydrogen, halogen, -C 4 alkyl, C r C 4 - alkoxy, C r C 4 alkylthio, -COOR 4, trifluoromethyl, nitro or cyano,
  • R j , R k and R m independently of one another are hydrogen or C 1 -C 4 -alkyl
  • R k and R m together are a C 4 -C 6 -alkylene bridge or an interrupted by oxygen, NH or -N (C- ⁇ -C 4 alkyl) - interrupted C 4 -C 6 alkylene, and
  • R n is C 1 -C 4 alkyl, phenyl or phenyl substituted by halogen, C 1 -C 4 alkyl, methoxy, nitro or trifluoromethyl; preferably safeners of the formula (S-VIII)
  • radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals can each be straight-chain or branched in the carbon skeleton.
  • Alkyl radicals, even in the composite meanings such as alkoxy, haloalkyl, etc., preferably have 1 to 4 carbon atoms and, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl.
  • Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals;
  • Alkenyl is for example AlII, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl.
  • Alkynyl means, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.
  • "(CrC 4 ) -Alkyr is the shorthand notation for alkyl of 1 to 4 carbon atoms, as well as other general definitions of radicals with bracketed ranges for the possible number of carbon atoms.
  • Cycloalkyl is preferably a cyclic alkyl radical having 3 to 8, preferably 3 to 7, particularly preferably 3 to 6, C atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Cycloalkenyl and cycloalkynyl refer to corresponding unsaturated compounds.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkinyl mean by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine, partially or fully substituted alkyl, alkenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF 2 CF 3 , CH 2 CHFCI , CCI 3 , CHCl 2 , CH 2 CH 2 Cl.
  • Haloalkoxy is eg OCF 3 , OCHF 2 , OCH 2 F, OCF 2 CF 3 , OCH 2 CF 3 and OCH 2 CH 2 Cl. The same applies to other halogen-substituted radicals.
  • a hydrocarbon radical may be an aromatic or an aliphatic hydrocarbon radical, where an aliphatic hydrocarbon radical is generally a straight-chain or branched saturated or unsaturated hydrocarbon radical, preferably having 1 to 18, particularly preferably 1 to 12, carbon atoms, for example alkyl, alkenyl or alkynyl ,
  • Aryl is generally a mono-, bi- or polycyclic aromatic system having preferably 6-20 C atoms, preferably 6 to 14 C atoms, more preferably 6 to 10 C atoms, e.g. Phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl and fluorenyl, more preferably phenyl.
  • Heterocyclic ring, heterocyclic radical or heterocyclyl means a mono-, bi- or polycyclic ring system which is saturated, unsaturated and / or aromatic and one or more, preferably 1 to 4, heteroatoms, preferably from the group N, S and O, contains.
  • saturated heterocycles having 3 to 7 ring atoms and one or two heteroatoms from the group N, O and S, wherein the chalcogens are not adjacent.
  • Particularly preferred are monocyclic rings having 3 to 7 ring atoms and a heteroatom from the group N, O and S, and morpholine, dioxolane, piperazine, imidazoline and oxazolidine.
  • Very particularly preferred saturated heterocycles are oxirane, pyrrolidone, morpholine and tetrahydrofuran.
  • partially unsaturated heterocycles having 5 to 7 ring atoms and one or two heteroatoms from the group N, O and S.
  • partially unsaturated heterocycles having 5 to 6 ring atoms and one heteroatom from the group N, O and S.
  • Very particular preferred partially unsaturated heterocycles are pyrazoline, imidazoline and isoxazoline.
  • heteroaryl e.g. mono- or bicyclic aromatic heterocycles having 5 to 6 ring atoms containing one to four heteroatoms from the group N, O, S, wherein the chalcogens are not adjacent.
  • monocyclic aromatic heterocycles having 5 to 6 ring atoms which contain a heteroatom from the group, N, O and S, and pyrimidine, pyrazine, pyridazine, oxazole, thiazole, thiadiazole, oxadiazole, pyrazole, triazole and isoxazole.
  • pyrazole, thiazole, triazole and furan are particularly preferred.
  • Substituted radicals such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, such as phenyl and arylalkyl, such as benzyl, or substituted heterocyclyl, represent a substituted radical derived from the unsubstituted radical, where the substituents are preferably one or more, preferably 1, 2 or 3 , in the case of Cl and F also up to the maximum possible number, substituents from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl , substituted amino such as acylamino, mono- and dialkylamino and alkylsulfinyl, haloalkylsulfinyl, alkylsulfon
  • Substituents from the group halogen for example fluorine or chlorine, (CrC 4 ) alkyl, preferably methyl or ethyl, (CrC 4 ) haloalkyl, preferably trifluoromethyl, (CrC 4 ) AIkOXy, preferably methoxy or ethoxy, (CrC 4 ) haloalkoxy, nitro and cyano.
  • substituents methyl, methoxy and chlorine are particularly preferred.
  • Mono- or disubstituted amino means a chemically stable radical from the group of substituted amino radicals which are N-substituted by, for example, one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles.
  • alkyl radicals having 1 to 4 carbon atoms are preferred.
  • Aryl is preferably phenyl.
  • Substituted aryl is preferably substituted phenyl.
  • acyl the definition mentioned further below applies, preferably (CrC 4) alkanoyl.
  • substituted hydroxylamino or hydrazino is preferably (CrC 4) alkanoyl.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times, in halogens such as Cl and F also up to five times, by identical or different radicals from the group halogen, (CrC 4 ) alkyl, (CrC 4 ) Alkoxy, (CrC 4 ) haloalkyl, (C r C 4 ) haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenols, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichloropheny
  • An acyl group means the residue of an organic acid preferably having up to 6 C atoms, e.g. the radical of a carboxylic acid and radicals derived therefrom, such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids, or the radical of carbonic acid monoesters, optionally N-substituted
  • Acyl is, for example, formyl, alkylcarbonyl, such as (C 1 -C 4 -alkyl) carbonyl, phenylcarbonyl, where the phenyl ring may be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl or N-alkyl-1 iminoalkyl.
  • stereoisomers which have the same topological linkage of the atoms, and mixtures thereof.
  • Such compounds contain one or more asymmetric C atoms or double bonds, which are not specified separately in the general formulas are.
  • the possible defined by their specific spatial form possible stereoisomers, such as enantiomers, diastereomers, Z and E isomers can be obtained by conventional methods from mixtures of stereoisomers or prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.
  • the compounds of formula (S-II) are e.g. from EP-A-0333131 (ZA-89/1960), EP-A-0269806 (US 4,891,057), EP-A-0346620 (AU-A-89/34951), EP-A-0174562, EP-A No.
  • the compounds of formula (S-IV) are known from numerous patent applications, for example US 4,021,224 and US 4,021,229.
  • Compounds of subgroup b) are further from CN-A-87/102789, EP-A-365484 and from "The Pesticide Manual", 11th to 13th edition, British Crop Protection Council and the Royal Society of Chemistry (1997), known.
  • the compounds of subgroup c) are described in WO-A-97/45016, those of subgroup d) in WO-A-99/16744 (in particular in EP-A-365484).
  • the cited documents contain detailed information on preparation processes and starting materials and name preferred compounds. These documents are expressly referred to, they are by quotation as part of this description.
  • the safeners of the above groups a) to e) reduce or prevent the phytotoxic effects which can occur when using the herbicidal compositions according to the invention in crops without impairing the effectiveness of the herbicides against harmful plants.
  • the field of application of the herbicides can be significantly extended and in particular by the use of safeners, the use of herbicides, which have so far only limited or could be used with insufficient success, ie of combinations without Safener in low dosages with little broad effect led to insufficient control of harmful plants, possible.
  • safeners in the formulations according to the invention, inter alia: 4-dichloroacetyl-1-oxa-4-aza-spiro [4.5] -decane (AD-67), 1-dichloroacetyl-hexahydro-3,3,8a-trimethylphenyl [ 1,2-a] -pyrimidine-6 (2H) -one (dicyclonone, BAS-145138), 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (Benoxacor), cloquintocet, 5-Chloro-quinolin-8-oxy-acetic acid (1-methylhexyl ester) (cloquintocet-mexyl), ⁇ - (cyanomethoxyimino) -phenylacetonitrile (cyometrinil), 2,2-dichloro-N- (2-oxo-2 - (2-propenylamino) -ethyl)
  • herbicide-safener mixtures are combinations of the following compounds with one another:
  • HPPD p-hydroxyphenyl pyruvate dioxygenase
  • d) compounds which act as safeners such as AD 67 (4- (dichloroacetyl) -1-oxa-4-azaspiro [4.5] decane), benoxacor, CL 304,415 (4-carboxymethylchroman-4-carboxylic acid), cloquintocet, Cloquintocet-mexyl, cyprosulfamides, dichloromide, dicyclonon, DKA-24 (N1, N2-diallyl-N2-dichloroacetylglycine amides), fenchlorazoles, fenchlorazoles-ethyl, fenclorim, flurazoles, fluxofenim, furilazoles, isoxadifen-ethyl, mefenpyr-diethyl, MW 191 ( 2-dichloromethyl-2-methyl-1,3-dioxolane), naphthalic anhydride (naphthalene-1,8-dicarboxylic
  • herbicides are combined, e.g. Fenoxaprop-p-ethyl + loxyniloctanoate, diclofopmethyl + bromoxyniloctanoate, CMPP + bromoxyniloctanoate, MCPA + loxyniloctanoate, bromoxyniloctanoate + bromoxynil heptanoate, bromoxyniloctanoate + bromoxynilheptanoate + MCPA, bromoxynil octanoate + bromoxynil-heptanoate + 2,4-D, phenmedipham + desmedipham, phenmedipham + desmedipham + ethofumesate, metamitron + ethofumesate, phenmedipham + ethofumesate + metamitron, fenoxaprop-p-ethyl + iodosul
  • Cyprosulfamide flupyrsulfuron + cyprosulfamide, pyrazosulfuron + cyprosulfamide, azimsulfuron + cyprosulfamide, bensulfuron + cyprosulfamide, bispyribac + cyprosulfamide, rimsulfuron + cyprosulfamide, tritosulfuron + cyprosulfamide, sulcotrione + cyprosulfamide, clomazone + cyprosulfamide, mesotrione + cyprosulfamide, topramezone + cyprosulfamide, metribuzin + cyprosulfamide, Bentazone + Cyprosulfamide, Bromoxynil + Cyprosulfamide, Propanil + Cyprosulfamide, Atrazine + Cyprosulfamide, Terbuthylazine + Cyprosulfamide, EPTC +
  • Cyprosulfamides acetochlor + cyprosulfamides, S-metolachlor + cyprosulfamides, flumioxazine + cyprosulfamides, flumiclorac + cyprosulfamides, fomesafen + cyprosulfamides, sulfentrazone + cyprosulfamides, dicamba + cyprosulfamides, MCPA + cyprosulfamides, MCPB + cyprosulfamides, 2,4-D + cyprosulfamides, clopyralid + Cyprosulfamide, Fluroxypyr + Cyprosulfamide, Picloram +
  • the weight ratio safener: herbicide can vary within wide limits and is preferably in the range from 1: 100 to 100: 1, in particular from 1: 100 to 50: 1, very particularly preferably from 1:10 to 10: 1
  • Herbicide (s) and safener (s) are usually dependent on the type of herbicide and / or the safener used and on the nature of the plant stock to be treated.
  • the agrochemically active compounds may also be fungicides, for example
  • Inhibitors of the respiratory chain complex I in particular diflumetorim
  • Respiratory chain complex II particularly boscalid, carboxin, fenfuram, flutolanil, furametpyr, mepronil, oxycarboxin,
  • Azoxystrobin Cyazofamide, Dimoxystrobin, Enestrobin, Famoxadone, Fenamidon, Fluoxastrobin, Kresoximethyl, Metominostrobin, Orysastrobin, Pyraclostrobin,
  • Decoupler especially dinocap, fluazinam Inhibitors of ATP production, in particular
  • Inhibitors of signal transduction in particular fenpiclonil, fludioxonil, quinoxyfen
  • Inhibitors of fat and membrane synthesis in particular chlozolinate, iprodione, procymidone, vinclozolin
  • Inhibitors of ergosterol biosynthesis in particular fenhexamide
  • Iminoctadinalesilate iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, metiram zinc, propineb, sulfur and sulfur preparations containing calcium polysulphide, thiram, tolylfluanid, zineb, ziram
  • the agrochemically active compounds may also be bactericides, for example bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • bactericides for example bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • the fungicides listed above are known, for example, from "The Pesticide Manual”, 12th edition (2000) and 13th edition (2003), The British Crop Protection Council or the references listed for the individual active ingredients.
  • the agrochemically active compounds may also be insecticides / acaricides and / or nematicides, for example
  • Acetylcholinesterase (AChE) inhibitors carbamates, for example alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, bendocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, dimetilane, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb , Isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl,
  • Pirimicarb promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC,
  • Organophosphates for example acephates, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos,
  • Sodium Channel Modulators / Voltage Dependent Sodium Channel Blockers Pyrethroids, for example, acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioethanomethrin, biopermethrin , Bioresmethrin, chlovaporthrin, cis-cypermethrin, cis
  • Oxadiazines for example Indoxacarb Semicarbazone, for example Metaflumizone (BAS3201)
  • Acetylcholine Receptor Agonists / Antagonists Chloronicotinyls, for example acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazines, thiacloprid, thiamethoxam
  • Nicotine, Bensultap, Cartap Acetylcholine receptor modulators Spinosyne, for example spinosad
  • GABA-Directed Chloride Channel Antagonists Organochlorines, for example Camphechlor, Chlordane, Endosulfan, Gamma-HCH, HCH, Heptachlor, Lindane, Methoxychlor Fiprole, for example Acetoprole, Ethiprole, Fipronil, Pyrafluprole, Pyriprole,
  • Mectins for example Abamectin, Emamectin, Emamectin benzoate, Ivermectin,
  • Juvenile hormone mimetics for example, diofenolan, epofenonans, fenoxycarb, hydroprene, kinoprenes, methoprenes, pyriproxifen, triprene
  • Diacylhydrazines for example chromafenozide, Halofenozide, Methoxyfenozide, Tebufenozide
  • Benzoylureas for example bistrifluron, chlorofluazuron, diflubenzuron, fluazuron,
  • Organotin compounds for example azocyclotin, cyhexatin, fenbutatin oxides
  • Pyrroles for example Chlorfenapyr dinitrophenols, for example binapacyrl, dinobutone, dinocap, DNOC
  • METI 1 S for example fenazaquin, fenpyroximate, pyrimidifen, pyridaben,
  • Inhibitors of fatty synthesis tetronic acids for example spirodiclofen, spiromesifen
  • Tetramic acids for example spirotetramat Carboxamides, for example flonicamide
  • Octopaminergic agonists for example, amitraz
  • Nereistoxin analogs for example thiocyclam hydrogen oxalate, thiosultap-sodium
  • Agonists of the ryanodine receptor benzoic acid dicarboxamides, for example flubendiamide
  • Anthranilamides for example DPX E2Y45 (3-bromo-N- ⁇ 4-chloro-2-methyl-6- [(methylamino) carbonyl] phenyl ⁇ -1- (3-chloropyridin-2-yl) -1H-pyrazole- 5-carboxamides)
  • Feed inhibitors for example cryolites, flonicamide, pymetrozine mite growth inhibitors, for example clofentezine, etoxazole, hexythiazox
  • insecticides listed above are e.g. known from "The Pesticide Manual", 12th edition (2000) and 13th edition (2003), The British Crop Protection Council or the references listed after the individual active ingredients.
  • a particular embodiment of the invention is the joint application of insecticides (acaricides, nematicides) as agrochemical active ingredients, either together or in succession.
  • agrochemically active compounds are used according to solubility in the present invention.
  • the criterion of water-soluble or oil-soluble can be understood by any active ingredient in the literature, e.g.
  • solubilities of agrochemicals are listed in "The Pesticide Manual", 12th edition (2000), 13th edition (2003) and 14th edition (2006), The British Crop Protection Council.
  • the sulfonylureas contained as component in the oil suspension concentrates according to the invention are always understood to mean all forms of use, such as acids, esters, salts and isomers, such as stereoisomers and optical isomers.
  • their salts are always to be understood, for example with inorganic and / or organic counterions.
  • sulfonylureas can form salts in which the hydrogen of the -S ⁇ 2 -NH group is replaced by a cation suitable for agriculture.
  • salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts or salts with organic amines.
  • salt formation can take place by addition of an acid to basic groups, such as, for example, amino and alkylamino.
  • Suitable acids for this purpose are strong inorganic and organic acids, for example HCl, HBr, H 2 SO 4 or HNO 3 .
  • Preferred esters are the alkyl esters, especially the CiC-io-alkyl esters such as methyl esters.
  • acyl radical means the radical of an organic acid which is formally formed by cleavage of an OH group from the organic acid, e.g. the radical of a carboxylic acid and radicals derived therefrom, such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radicals of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
  • An acyl radical is preferably formyl or acyl from the group CO-R Z, CS-R Z, CO-OR 2, CS-OR 2, CS-SR 2, SOR Z or SO 2 R 2, wherein R 2 are each a C 1 -C 10 - hydrocarbon radical such as C 1 -C 10 -alkyl or C 6 -C 10 -aryl which is unsubstituted or substituted, for example by one or more substituents from the group halogen such as F, Cl, Br, I, alkoxy, haloalkoxy, Hydroxy, amino, nitro, cyano or alkylthio, or R 2 means aminocarbonyl or aminosulfonyl, where the latter two radicals are unsubstituted, N-monosubstituted or N, N-disubstituted, for example by substituents from the group alkyl or aryl.
  • Acyl is, for example, formyl, haloalkylcarbonyl,
  • alkyloxycarbonyl such as (CrC 4) alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, such as (CrC 4) alkylsulfonyl,
  • a hydrocarbon radical means a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl.
  • a hydrocarbon radical preferably has 1 to 40 C atoms, preferably 1 to 30 C atoms; particularly preferably a hydrocarbon radical is alkyl, alkenyl or alkynyl having up to 12 C atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
  • Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl.
  • a heterocyclic radical or ring may be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more heteroatoms in the ring, preferably from the group N, O and S; it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms.
  • the heterocyclic radical may be e.g. a heteroaromatic radical or ring (heteroaryl), e.g.
  • a mono-, bi- or polycyclic aromatic system in which at least one ring contains one or more heteroatoms for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is partially or fully hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, triazolyl, dioxolanyl, morpholinyl, tetrahydrofuryl.
  • heteroatoms for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imi
  • Suitable substituents for a substituted heterocyclic radical are the substituents mentioned below in question, in addition also oxo.
  • the oxo group may also be attached to the hetero ring atoms, which may exist in different oxidation states, e.g. at N and S, occur.
  • Substituted radicals such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, represent, for example, a substituted radical derived from the unsubstituted radical, where the substituents are, for example, one or more, preferably 1, 2 or 3 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and,
  • radicals with C atoms those having 1 to 4 C atoms, in particular 1 or 2 C atoms, are preferred.
  • Preferred are in the Generally given to substituents from the group halogen, for example fluorine and chlorine, (Ci-C 4) alkyl, preferably methyl or ethyl, (CrC 4) haloalkyl, preferably trifluoromethyl, (CrC 4) -alkoxy, preferably methoxy or ethoxy, (Ci-C 4 Haloalkoxy, nitro and cyano.
  • substituents methyl, methoxy and chlorine.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals, preferably from the group comprising halogen, (CrC 4) alkyl, (Ci-C 4) alkoxy, (CrC 4) haloalkyl , (C 1 -C 4 ) -haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -T ⁇ ichlorphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
  • Cycloalkyl means a carbocyclic saturated ring system preferably having 3-6 C atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • the carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals in the carbon skeleton in each case be straight-chain or branched. Unless specifically stated, these radicals are the lower carbon skeletons, e.g. with 1 to 6 C atoms or with unsaturated groups having 2 to 6 C atoms, preferred.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean e.g.
  • Alkynyl means e.g. Propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methyl-but-3-yn-1-yl.
  • Halogen is, for example, fluorine, chlorine, bromine or iodine.
  • Haloalkyl, alkenyl and alkynyl are alkyl which is partially or completely substituted by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine, Alkenyl or alkynyl, eg CF 3 , CHF 2 , CH 2 F, CF 3 CF 2 , CH 2 FCHCl, CCI 3 , CHCl 2 , CH 2 CH 2 Cl;
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 Cl; the same applies to haloalkenyl and other halogen-substituted radicals.
  • compositions according to the invention contain, in addition to components a) and b), one or more auxiliaries and additives, for example:
  • auxiliaries such as defoamers, antifreeze agents, evaporation inhibitors, preservatives, fragrances, dyes, stabilizers, water scavengers or thickeners,
  • one or more surfactants may be present in the formulations according to the invention as component c). These may be monomeric or polymeric (eg, graft polymers).
  • components c) are surfactants based on silicone, such as trisiloxane surfactants, derivatives of polydimethylsiloxanes and / or silicone oils, or sugar-based surfactants, such as Atplus 309 ® F (Uniqema).
  • components c) are (C 4 -C 3 o) (poly) alkylene oxide adducts which may be branched, for example, can be linear, saturated or unsaturated, in particular of fatty alcohols and / or fatty acids or Fettklareestern.
  • (poly) alkylene oxide adducts are Soprophor CY8 ® (Rhodia), Genapol ® X-060, Genapol ® X-080, Genapol ® X-150;
  • component c) are in the continuous phase of the formulation insoluble components, for example anionogenic surfactants, such as Hostapur ® OSB (Clariant), Netzer IS ® (Clariant), Galoryl DT 201 ® (CFPI), Tamol ® (BASF) or Morwet ® D 425 (Witco) may be used.
  • anionogenic surfactants such as Hostapur ® OSB (Clariant), Netzer IS ® (Clariant), Galoryl DT 201 ® (CFPI), Tamol ® (BASF) or Morwet ® D 425 (Witco) may be used.
  • component c) also sulfosuccinates, e.g. be of the formula (III),
  • R 1, R 2 independently of one another, identically or differently an unsubstituted or substituted Ci-C 3 o-hydrocarbon radical such as -C 3 O-alkyl, or a (poly) alkylene oxide adduct, and
  • M p is a cation, for example a metal cation such as an alkali or alkaline earth metal cation, an ammonium cation such as NH 4 , alkyl, alkylaryl or poly (arylalkyl) phenylammonium cation or their (poly) alkylene oxide adducts, or an amino-terminated (poly) alkylene oxide adduct ,
  • a metal cation such as an alkali or alkaline earth metal cation
  • an ammonium cation such as NH 4
  • an amino-terminated (poly) alkylene oxide adduct for example a metal cation such as an alkali or alkaline earth metal cation, an ammonium cation such as NH 4 , alkyl, alky
  • (Poly) alkylene oxide adducts in the context of this specification are reaction products of alkoxylatable starting materials such as alcohols, amines, carboxylic acids such as fatty acids, hydroxy- or amino-functional carboxylic acid esters (for example triglycerides based on castor oil) or carboxylic acid amides with alkylene oxides, where the (poly) alkylene oxide adducts have at least one alkylene oxide unit but are generally polymeric, ie 2-200, preferably 5-150 alkylene oxide
  • alkylene oxide units ethylene oxide, propylene oxide and butylene oxide units, especially ethylene oxide units, are preferred.
  • the described (poly) alkylene oxide adducts can be made from identical or different alkylene oxides, for example from blocky or random arranged ethylene oxide and propylene oxide, so that the present application also includes such mixed alkylene oxide adducts.
  • component c) may also contain non-surfactant polymers, e.g. Polyvinyl alcohols, polyacrylates, polymalinates or polyethylene oxides.
  • non-surfactant polymers e.g. Polyvinyl alcohols, polyacrylates, polymalinates or polyethylene oxides.
  • the polymers contained as component c) may be inorganic (e.g., silicates, phosphates) or organic, cationic, anionic, or neutral, synthetic, or naturally occurring.
  • the formulations according to the invention as component d) may contain various organic solvents such as non-polar solvents, polar protic or aprotic dipolar solvents and mixtures thereof.
  • organic solvents d) are - aliphatic or aromatic hydrocarbons, for example mineral oils, paraffins or toluene, xylenes and naphthalene derivatives, in particular 1-methylnaphthalene, 2-methylnaphthalene, C ⁇ -Ci ⁇ -aromatics such as the Solvesso ® series (ESSO), for example with the types Solvesso ® 100 (bp 162-177 0 C), Solvesso ® 150 (bp 187-207 0 C) and Solvesso ® 200 (bp 219-282 0 C) and C 6 -C 2 o-aliphatic, which can be linear or cyclic, such as the products of the Shellsol ® series,
  • Esters such as triacetin (acetic acid triglyceride), butyrolactone, propylene carbonate, triethyl citrate, and phthalic acid (C 1 -C 22 ) alkyl esters, especially phthalic acid (Cr
  • Ce alkyl esters, maleic acid (Ci-C 13 ) alkyl esters, linear, branched, saturated or unsaturated C 1 -C 20 alcohols such as methanol, ethanol, n- and iso-propanol, n-, iso-, sec- and tert.
  • Alkylenglykolmonoalkyether and -dialkylether such as propylene glycol monomethyl ether, especially Dowanol ® PM (propylene glycol monomethyl ether), propylene glycol monoethyl ether, ethylene glycol monomethyl ether or - monoethyl ether, diglyme and tetraglyme, Amides such as dimethylformamide (DMF) 1 dimethylacetamide, dimethylcapryl / caprin-fatty acid amide and N-alkylpyrrolidones, ketones such as the water-soluble acetone, but also water-immiscible ketones such as cyclohexanone or isophorone, - nitriles such as acetonitrile, propionitrile, butyronitrile and benzonitrile,
  • Sulfoxides and sulfones such as dimethyl sulfoxide (DMSO) and sulfolane, as well as oils in general, such as mineral oils or vegetable-based oils such as corn oil, linseed oil and rapeseed oil.
  • DMSO dimethyl sulfoxide
  • oils in general such as mineral oils or vegetable-based oils such as corn oil, linseed oil and rapeseed oil.
  • preferred organic solvents for the purposes of the present invention are ester oils such as rapeseed oil methyl ester and aliphatic or aromatic hydrocarbons, such as Solvesso ® types, z. Solvesso ® 200,
  • polycarboxylic can act as a solvent and are z.
  • Carboxylic acids preferably with 2-20 C atoms in question. Also suitable are polymeric polycarboxylic acids, preferably having molecular weights of up to 2000 g / mol.
  • polycarboxylic acids are oxalic, malonic, succinic, glutaric, adipic, pimelic, sebacic, azelaic, suberic, maleic, phthalic, terephthalic, mellitic, trimellitic, polymaleic, polyacrylic - and polymethacrylic acid and co- or
  • alkyl alcohols preferably monofunctional alkyl alcohols having 1 - 20 C atoms in question.
  • alkyl alcohols are methyl, ethyl-n-propyl, iso-propyl, n-butyl, sec-butyl, isobutyl or tert-butyl alcohol.
  • the polycarboxylic acid alkyl esters preferably have the following formula (I)
  • R ⁇ and R p are identical or different and are H, an unsubstituted or substituted C 1 -C 20 -hydrocarbon radical such as C 1 -C 10 -alkyl or a group (CR'R'VCO-OR ''', where R' and R '' are identical or differently, H or an unsubstituted or substituted Ci-C 2 o-hydrocarbon radical, such as Ci-Cio-alkyl, y is an integer from 0 to 10 and R '"is an unsubstituted or substituted C 1 -C 20 -
  • Hydrocarbon radical such as C 1 -C 0 alkyl
  • Rv and R ⁇ are identical or different unsubstituted or substituted C1 to C 20 - hydrocarbon radical such as C1-C1 0 alkyl, and x is a whole number from 0 to 20th
  • Particularly preferred polycarboxylic acid alkyl esters are diesters of the following
  • x is an integer from 0 to 20
  • Rv and R ⁇ independently Ci-C 6 alkyl are the same or different.
  • polycarboxylic acid alkyl esters examples include oxalic acid esters, such as dimethyl oxalate, diethyl oxalate, di-n-propyl oxalate, diisopropyl oxalate and methyl ethyl oxalate, malonic esters, such as dimethyl malonate, diethyl malonate, di-n-propyl malonic acid, Malonic acid diisopropyl ester and methyl malonate, succinic esters such as succinic acid dimethyl ester, succinic acid diethyl ester, succinic di-n-propyl ester, succinic diisopropyl ester and methyl succinate, glutaric acid esters such as dimethyl glutarate, glutaric acid diethyl ester, glutaric acid di-n-propyl ester, glutaric acid di-isopropyl ester and methyl glutarate, and adipic acid esters
  • Carboxylic acids with the alcohols accessible can be obtained by the reaction of "activated" polycarboxylic acids such as polycarboxylic acid anhydrides or polycarboxylic acid (poly) chlorides with the alcohols by known esterification methods.
  • the liquid formulations according to the invention may contain as component e) various agrochemicals. These are, for example, growth regulators or fertilizers.
  • component f) may also contain customary formulation auxiliaries, such as defoamers, antifreeze agents, evaporation inhibitors, preservatives, fragrances, dyes, stabilizers, water scavengers or thickeners.
  • Preferred formulation auxiliaries are antifreeze agents and evaporation inhibitors such as glycerol, for example in an amount of 2 to 10 wt .-%, and preservatives, for example Mergal K9N ® (Riedel) or Cobate ® C.
  • Tank-mix components may also be present in the formulations according to the invention as component g). Examples of this are tank mixers
  • Adjuvants such as Telmion ® (Hoechst) or vegetable oils such as Actirob B ® (Novance) or Hasten ® (Victorian Chemicals), inorganic compounds such as fertilizers, eg. As ammonium sulfate, ammonium nitrate, ammonium hydrogen sulfate, ureas or hydrotropes.
  • the active ingredient content of the formulations according to the invention can generally be between 0.001% by weight and 80% by weight, and in individual cases, in particular when using several active substances, higher loadings are also possible.
  • auxiliaries and additives which can be used to prepare the formulations according to the invention are known in principle and are described, for example, in: McCutcheon 's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface active agents, Chem., Publ.Co.ln ⁇ , NY 1964, Schonfeldt, "Grenz vomitepte ⁇ thylenoxidaddukte", Wiss. Verlagsgesellschaft, Stuttgart 1976, Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hanser Verlag, Kunststoff, 4th edition 1986.
  • the present invention thus also encompasses the processes described for the preparation of the formulations according to the invention.
  • the formulations according to the invention are physically and chemically stable formulations which, when diluted with water, give spray mixtures having physically-favorable application properties.
  • the formulations of the invention have favorable biological properties and are widely used, for. B. to combat undesirable plant growth.
  • the preparation of the microcapsules can be prepared analogously to known processes.
  • the preparation of the encapsulated aqueous solutions or suspensions are preferably prepared starting from a water-in-oil emulsion with the addition of polymerizable components, if appropriate in the presence of suitable surface-active components, see, for example, US Pat. Nos. 4,157,983 and 4,534,783.
  • formulations according to the invention can be prepared, for example, as follows (exemplary embodiment):
  • An organic phase was prepared by dissolving dodecylbenzenesulfonic acid and nonionic alkylarylphenol in kerosene as a solvent.
  • the aqueous phase was prepared by dissolving glyphosate and urea / formaldehyde prepolymers in water. The two phases were then combined to form a water-in-oil emulsion with stirring. Thereafter, the temperature was raised to 40 0 C and stirring continued for 2 or more hours. The resulting product was cooled to give a suspension of microcapsules in the organic phase, the microcapsules enclosing the aqueous medium.
  • the production of microcapsules which include dissolved or dispersed in the oil phase agrochemical active ingredients can be carried out analogously to the known methods.
  • the water-soluble and microencapsulated agrochemical active ingredients are mixed with the agrochemical active substances dissolved or dispersed in the oil phase to give the oil suspension concentrate according to the invention.
  • the preparation of the oil suspension concentrates according to the invention is also provided. These can be prepared by known methods. The grinding and mixing of the components takes place as far as this is compatible with the formation or presence of the microcapsules according to the known methods.
  • the oil suspension concentrates of the present invention may optionally be diluted in conventional manner (e.g., by water), e.g. to suspensions, emulsions, suspoemulsions or solutions, preferably to emulsions. It may be advantageous to obtain spray mixtures which contain further agrochemical active substances (for example tank mix partners in the form of corresponding formulations) and / or customary auxiliaries and additives, for example self-emulsifying oils such as vegetable oils or paraffin oils and / or fertilizers.
  • the present invention therefore also relates to such herbicidal compositions, based on the oil suspension concentrates according to the invention.
  • herbicidal compositions according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants, including species which are resistant to herbicidal active compounds such as glyphosate, glufosinate, atrazine or imidazolinone herbicides.
  • herbicidal active compounds such as glyphosate, glufosinate, atrazine or imidazolinone herbicides.
  • the hard-to-control perennial weeds that expel from rhizomes, rhizomes or other permanent organs are well detected by the active ingredients. or post-emergence.
  • the application is preferably carried out on the accumulated harmful plants (for example, weeds or unwanted crops), in particular before emergence of the (desired) crops.
  • some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain
  • the spectrum of activity extends to species such as e.g. Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp., Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharitis spp., Polygonum spp., Sida spp., Sinapis spp , Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., on the annual side, as well as Convolvulus, Cirsium, Rumex, and Artemisia in perennial weeds.
  • species such as e.g. Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp., Ipomoea
  • herbicidal compositions according to the invention are applied to the surface of the earth before germination, either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die completely after three to four weeks.
  • the herbicidal compositions according to the invention are distinguished by a rapidly onset and long-lasting herbicidal action.
  • the rainfastness of the active ingredients in the combinations according to the invention is generally favorable.
  • a particular advantage is the fact that the used and effective dosages of compounds (a) can be set so low that their soil effect is optimally low. Thus, their use is not only possible in sensitive cultures, but groundwater contamination is virtually avoided.
  • the combination of active substances according to the invention enables a considerable reduction in the required application rate of the active ingredients.
  • the agents according to the invention have in some cases outstanding growth-regulatory properties in the crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant constituents and facilitate harvesting, such as be used by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of unwanted vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous cultures, as storage can be reduced or completely prevented.
  • the agents for combating harmful plants can be used in known plant crops or tolerant or genetically modified crops to be developed.
  • the transgenic plants are usually characterized by particular advantageous properties, in addition to the resistance to the inventive compositions, for example, by resistance to plant diseases or pathogens of plant diseases like certain insects or microorganisms like fungi, bacteria or viruses.
  • Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients.
  • one of the oil suspension concentrates according to the invention is used in the context of a method for controlling harmful organisms, wherein the application to the harmful organisms takes place in those places where these occur.
  • the use of one of the oil suspension concentrates according to the invention for controlling harmful organisms is within the scope of the invention.
  • the sulfonylurea-containing oil suspension concentrates are e.g. to
  • Control of harmful plants in crops suitable, for example in economically important arable crops such as monocotyledonous crops such as cereals (eg wheat, barley, rye, oats), rice, corn, millet, or dicotyledonous crops such as sugar beet, oilseed rape, cotton, sunflowers and legumes such as the genera Glycine (eg Glycine max.
  • monocotyledonous crops such as cereals (eg wheat, barley, rye, oats), rice, corn, millet, or dicotyledonous crops such as sugar beet, oilseed rape, cotton, sunflowers and legumes
  • Glycine eg Glycine max.
  • Soy as non-transgenic Glycine max (eg conventional varieties such as STS varieties) or transgenic Glycine max (eg RR soy or LL soy) and their crosses), Phaseolus, Pisum, Vicia and arachis, or vegetable crops from various botanical groups such as potato, leek, cabbage, carrot, tomato, onion, as well as permanent and Plantation crops such as pome and stone fruit, soft fruit, wine, Hevea, bananas, sugarcane, coffee, tea, citrus, nut orchards, roses, palm tree and forest crops. For the application of herbicide combinations, these cultures are also preferred.
  • herbivory tolerant mutant cultures and tolerant transgenic crops preferably maize, rice, cereals, rapeseed and soybean, in particular soybean, which are resistant to imidazolinone herbicides, glufosinates or glyphosates.
  • the oil suspension concentrates may also be used non-selectively to control undesired plant growth, e.g. in permanent and plantation crops, on roadsides, squares, industrial plants, airfields or railway facilities, or for so-called burn-down application, e.g. in crops, e.g. monocotyledonous crops such as cereals (e.g., wheat, barley, rye, oats), rice, corn, millet, or dicotyledonous crops such as cereals (e.g., wheat, barley, rye, oats), rice, corn, millet, or dicotyledonous crops such as
  • Glycine eg Glycine max. (soy) as non-transgenic Glycine max (eg conventional varieties such as STS varieties) or transgenic Glycine max (eg RR soy or LL soy) and their crosses
  • Phaseolus Phaseolus
  • Pisum Phaseolus
  • Vicia Triangulose
  • Arachis or vegetable crops from various botanical groups such as potato, leek, cabbage, carrot, tomato, onion.
  • Table 1 shows the composition of an oil suspension concentrate according to the invention, wherein both a component (a) and a component (b) is encapsulated.
  • Table 2 shows a composition in which only component (a) is encapsulated.

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Abstract

L'invention concerne un concentré de suspension huileuse contenant (a) une ou plusieurs substances actives agrochimiques dans la phase aqueuse présente sous une forme encapsulée dans la phase huileuse, et (b) une ou plusieurs substances actives agrochimiques encapsulées dans la phase huileuse, présentes en même temps que des adjuvants et des additifs usuels.
EP08701053A 2007-01-23 2008-01-10 Concentre de suspension huileuse comprenant des substances actives agrochimiques micro-encapsulees Withdrawn EP2111104A2 (fr)

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EP07001380A EP1952688A1 (fr) 2007-01-23 2007-01-23 Concentré de suspension à huile comprenant des agents actifs agrochimiques microencapsulés et non microencapsulés
PCT/EP2008/000126 WO2008089890A2 (fr) 2007-01-23 2008-01-10 Concentré de suspension huileuse comprenant des substances actives agrochimiques micro-encapsulées
EP08701053A EP2111104A2 (fr) 2007-01-23 2008-01-10 Concentre de suspension huileuse comprenant des substances actives agrochimiques micro-encapsulees

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EA (1) EA013316B1 (fr)
EC (1) ECSP099527A (fr)
IL (1) IL199960A0 (fr)
MX (1) MX2009007824A (fr)
UA (1) UA96009C2 (fr)
WO (1) WO2008089890A2 (fr)

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BRPI0807401A2 (pt) 2014-05-27
IL199960A0 (en) 2010-04-15
JP2010516720A (ja) 2010-05-20
WO2008089890A3 (fr) 2009-05-22
AR064982A1 (es) 2009-05-06
CA2676210A1 (fr) 2008-07-31
AU2008209129A1 (en) 2008-07-31
EA200900855A1 (ru) 2009-12-30
WO2008089890A2 (fr) 2008-07-31
EP1952688A1 (fr) 2008-08-06
US20080176746A1 (en) 2008-07-24
EA013316B1 (ru) 2010-04-30
CN101621924A (zh) 2010-01-06
UA96009C2 (ru) 2011-09-26
KR20090113864A (ko) 2009-11-02
MX2009007824A (es) 2009-07-30
ECSP099527A (es) 2009-08-28

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